固体甲基铝氧烷用于负载茂金属催化剂的研究

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摘要在烯烃聚合领域,甲基铝氧烷(MAO)是茂金属催化剂体系中最常用的助催化剂。本研究以苯甲酸催化三甲基铝(TMA)受控水解生成甲基铝氧烷(MAO),经热解过程后合成了一种不溶形式的固体聚甲基铝氧烷(sMAO)。系统考察了制备过程条件如前驱体三甲基铝浓度、热解温度、己烷用量等对产品sMAO形貌的影响规律。利用扫描电镜、电感耦合等离子体质谱仪、激光粒度分布仪等手段对sMAO进行了分析表征。sMAO可以作为载体负载茂金属化合物,用于乙烯淤浆聚合反应。以rac-乙烯双(1-茚基)二氯化锆为茂金属活性组分,将其固定化于sMAO载体上,可在己烷溶剂中获得极高的催化聚合活性,与传统硅胶负载茂金属催化剂相比提高了4~5倍。

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	邬超凡
	臧瑾瑾
	王立娟
	李健

关键词：固体甲基铝氧烷茂金属催化剂聚乙烯淤浆聚合

Abstract： Methylaluminoxane (MAO) is the most commonly used activator for metallocenes in olefin polymerization reactions. In this research, an insoluble form of methylaluminoxane, also known as solid polymethylaluminoxane (sMAO), has been synthesized by the controlled hydrolysis of trimethylaluminum (TMA) with benzoic acid, followed by thermolysis. The role of preparing conditions (concentration of precursor, temperature of thermolysis, amount of hexane, et al.) on the particular morphology was systematically explored. SEM, ICP-MS and PSDA were used to characterize sMAO particles. sMAO can be utilized to support metallocene pre-catalysts in slurryphase ethylene polymerization reactions. Metallocene pre-catalyst rac-ethylenebis(1-indenyl)dichlorozirconium, rac-(EBI)ZrCl₂ were immobilized on sMAO samples, to afford solids which showed very high polymerization activities in hexane, comparable to those of the respective homogeneous catalysts formed by treatment of the pre-catalysts with MAO.

Keywords： solid polymethylaluminoxane metallocene catalyst polyethylene slurry polymerization

Received 2022-11-08;

Fund:中国石油天然气股份有限公司科学研究与计划开发项目(2022ZG17,2020B-2620,2020B-2621)。

Corresponding Authors: 李健,副教授,E-mail:lijian@tust.edu.cn。 Email: lijian@tust.edu.cn

About author: 邬超凡(1997-),男,硕士研究生,现从事负载型茂金属催化剂方面的研究。

引用本文:

邬超凡, 臧瑾瑾, 王立娟, 李健.固体甲基铝氧烷用于负载茂金属催化剂的研究[J]. 化学工业与工程, 2024,41(3): 56-67

WU Chaofan, ZANG Jinjin, WANG Lijuan, LI Jian.Solid MAO supported metallocene catalyst for slurry polymerization of ethylene[J]. Chemcial Industry and Engineering, 2024,41(3): 56-67

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